Aqueous solutions of α-cyclodextrin (α-CD) and polyethylene glycol (PEG) form interesting complexes,
where several α-CD units are penetrated by the linear polymeric PEG chain and produce a so-called
“polyrotaxane”. This supramolecular structure is stabilized by strong interactions between the α-CD
hydrophobic internal cavity and the -CH2OCH2- moieties of PEG. When cyclodextrins have occupied
the whole PEG chain, the polyrotaxanes aggregate and precipitate, forming a thick solid gel. Turbidity
measurements at λ=400 nm were used to study the threading phenomenon. The temperature of the
solution and the composition of the solvent affect the formation of polyrotaxanes in a significant way. We
propose a molecular model to explain the experimental findings in terms of a multistep threading process.
The Gibbs free energy related to the formation of polyrotaxanes is calculated according to the transition
state theory.

Aqueous solutions of α-cyclodextrin (α-CD) and polyethylene glycol (PEG) form interesting complexes,
where several α-CD units are penetrated by the linear polymeric PEG chain and produce a so-called
“polyrotaxane”. This supramolecular structure is stabilized by strong interactions between the α-CD
hydrophobic internal cavity and the -CH2OCH2- moieties of PEG. When cyclodextrins have occupied
the whole PEG chain, the polyrotaxanes aggregate and precipitate, forming a thick solid gel. Turbidity
measurements at λ=400 nm were used to study the threading phenomenon. The temperature of the
solution and the composition of the solvent affect the formation of polyrotaxanes in a significant way. We
propose a molecular model to explain the experimental findings in terms of a multistep threading process.
The Gibbs free energy related to the formation of polyrotaxanes is calculated according to the transition
state theory.